The paper refers to the problem of separation of the overlapping signals in voltammetry, which was resolved by the assumption that the univariate calibration models for the individual analytes are requested. It was demonstrated that Independent Components Analysis (ICA) is an effective tool for reconstruction of the successive signals shape, peak positions and also the basic validation parameters meet the typical criteria. Simulation approach enabled selection of the optimal set of mixtures, necessary for the effective operation of the ICA and high predictive ability of the calibration models. It was proved that the triples of analytes chosen from the list of four phenolic acids, ie. caffeic of 9.9 -87.6 mu M, ferulic of 5.9 -52.6 mu M, syringic of 9.9 -87.3 mu M, and vanillic acid of 13.9 -122.7 mu M may be successfully simultaneously determined by differential pulse voltammetry on boron doped diamond electrode, excluding samples at concentrations close to the lower limit of linearity. (C) 2016 The Electrochemical Society. All rights reserved.